The reaction was stirred at room temperature 30 min then MeI
(4.0 mmol, 250 lL) was added dropwise. The reaction was
stirred at room temperature overnight then evaporated under
vacuum. The resulting powder was dissolved in DMF (6 mL)
then Et3N (0.16 mmol, 23 lL) was added and the mixture stirred
at room temperature for 1 h. Isopropanol (8 mL) and diethyl
ether were added. The precipitate was filtrated, dissolved in
MeOH and precipitated again with diethyl ether. Iodide anions
were exchanged by chloride ions over an Amberlite IRA-900
resin in MeOH solution, and finally precipitated after filtration
by addition of diethyl ether. The crude product was dried for
several hours and the expected compound was obtained in 77%
yield (83 mg). dH (500.13 MHz, DMSO-d6, 343 K) −2.66 (2H, s,
-NHpyr), −2.55 (2H, broad s), −0.71 (2H, broad s), −0.41 (2H,
broad s), 0.66 (2H, broad t, J = 7,5), 0.76 (2H, broad s), 1.30 (2H,
broad s), 1.38 (2H, broad s), 1.58 (4H, broad s), 1.70 (2H, m), 2.10
(2H, m), 2.38 (2H, broad t, J = 10.6), 2.88 (2H, broad s), 3.01 (2H,
broad d, J = 8.5), 4.41 (6H, s, -Pyr+-CH3), 7.54 (2H, t, J = 7.8,
Haro), 7.57 (2H, t, J = 7.8, Haro), 7.74 (2H, d, J = 8.0, Haro), 7.79
(4H, t, J = 7.7, Haro), 7.84 (2H, t, J = 7.4, Haro), 7.99 (4H, d, J =
6.0, H3pyridine), 8.03 (d, 2H, J = 7.4 Hz, Haro), 8.23 (2H, d, J = 7.7,
Haro), 8.48 (2H, s, Hbpyr), 8.50 (2H, s, -NHCO), 8.63 (2H, d, J =
4.6, Hbpyr), 8.74 (2H, s, Hbpyr), 8.77 (2H, d, J = 4.6, Hbpyr), 9.08 (4H,
d, J = 6.01, H2pyridine), 9.55 (2H, s, -NHCO); m/z (ESI HRMS)
638.2887 ([M]++ C76H72N14O6 requires 638.2879); kmax(phosphate
buffer, pH 7.4)/nm (10−3e/dm3 mol−1 cm−1) 417.0 (333.1), 514.0
(15.8), 547.5 (3.4), 587.5 (4.6), 643.5 (1.4).
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6Fe
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In a dry-box, a solution of porphyrin 6 (0.007 mmol, 10 mg)
in DMF (6 mL) was added iron(II) bromide (0.1 mmol, 20 mg).
◦
The mixture was stirred for one day at 120 C, then solvent was
evaporated. The resulting powder was dissolved in a methanol–
THF mixture, then pentane was added. The precipitate was
filtrated, washed with THF and dried for several hours. m/z
(ESI HRMS) 665.2480 ([M]++ C76H70N14O656Fe requires 665.2476);
Soret (kmax, phosphate buffer pH 7.4): 6Fe + pyridine: 424 nm, +
O2: 420 nm.
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20 D. Ricard, M. L’Her, P. Richard and B. Boitrel, Chem.–Eur. J., 2001,
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1604 | Org. Biomol. Chem., 2007, 5, 1601–1604
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